Butadiene polymers having terminal functional groups

ABSTRACT

Hydrogenated butadiene polymers having terminal functional groups have minimum viscosity at any molecular weight when the 1,2-addition is between 30% and 70%. Hydrogenated butadiene polymers having about two terminal hydroxyl groups per molecule have surprisingly lower viscosities at 30% to 70% 1,2-addition than similar polymers having either higher or lower amounts of 1,2-addition. The polymers are useful in making coatings, sealants, binders, and block copolymers with polyesters, polyamides, and polycarbonates.

BACKGROUND OF THE INVENTION

This invention relates to manufacture of low viscosity hydrogenatedbutadiene polymers having terminal functional groups and use of the lowviscosity polymers to make coatings and other high molecular weightpolymers.

Anionic polymerization of conjugated dienes with lithium initiators,such as sec-butyllithium, and hydrogenation of residual unsaturation hasbeen described in many references including U. S. Pat. No. Re. 27,145which teaches a relationship between the amount of 1,2-addition ofbutadiene (35% to 55% ) and the glass transition temperatures of thehydrogenated butadiene polymers.

The termination of living anionic polymers to form functional end groupsis described in U.S. Pat. Nos. 4,417,029, 4,518,753, and 4,753,991. Ofparticular interest for the present invention are terminal hydroxyl,carboxyl, phenol, epoxy, and amine groups.

For unsaturated 1,3-butadiene polymers it is known that low 1,2-additionis necessary to obtain low viscosity as taught in U.S. Pat. Nos.4,518,753 and 3,652,732. However, when these polymers are hydrogenatedthey are crystalline solids. Such a crystalline polymer is availablefrom Mitsubishi and is designated POLYTAIL H polymer which has a meltingpoint of 72° C.

The hydrogenated butadiene polymers are non-crystalline when the1,2-addition of butadiene is above 30% as described in U.S. Pat. No.4,020,125. The non-crystalline hydrogenated butadiene polymers areviscous liquids at low molecular weights as described in U.S. Pat. Nos.4,866,120 and 4,020,125. POLYTAIL HA polymer produced by Mitsubishi andNISSO GI-2000 polymer produced by Nippon Soda are commercial examples oflow molecular weight hydrogenated butadiene polymers which have terminalfunctional groups and 1,2-addition of about of 84%.

It is an object of the present invention to provide hydrogenatedbutadiene polymers having terminal functional groups and low viscosityat room temperature. It is also an object of the invention to use thelow viscosity polymers to make coatings and other high molecular weightpolymers.

SUMMARY OF THE INVENTION

Applicants have discovered that varying the amount of 1,2-addition ofbutadiene in hydrogenated butadiene polymers having terminal functionalgroups significantly and unexpectedly impacts the viscosity of thepolymers. The lowest viscosity for any given molecular weight of ahydrogenated butadiene polymer having terminal functional groups isachieved when the 1,2-addition is between 30% and 70%, preferablybetween 40% and 60%.

The hydrogenated butadiene polymers of the invention may be used withoutsolvents at room temperature when the peak molecular weight, as measuredby gel permeation chromatography, is between 500 and 20,000, preferablybetween 1,000 and 10,000.

DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot of the relationship between vinyl content and viscosityof hydrogenated 1,3-butadiene polymers having terminal functionalgroups. The viscosity data are adjusted to remove molecular weightcontributions by dividing the viscosity by the peak molecular weightraised to the 3.4 power.

DETAILED DESCRIPTION OF THE INVENTION

Anionic polymerization of conjugated diene hydrocarbons with lithiuminitiators is well known as described in U.S. Pat. Nos. 4,039,593 andRe. 27,145 which descriptions are incorporated herein by reference.Polymerization commences with a monolithium, dilithium, or polylithiuminitiator which builds a living polymer backbone at each lithium site.Typical living polymer structures containing polymerized conjugateddiene hydrocarbons are:

X--B--Li

X--A--B--Li

X--A--B--A--Li

Li--B--Y--B--Li

Li--A--B--Y--B--A--Li

wherein B represents polymerized units of one or more conjugated dienehydrocarbons such as butadiene or isoprene, A represents polymerizedunits of one or more vinyl aromatic compounds such as styrene, X is theresidue of a monolithium initiator such as sec-butyllithium, and Y isthe residue of a dilithium initiator such as the diadduct ofsec-butyllithium and m-diisopropenylbenzene. Some structures, includingthose pertaining to polylithium initiators or random units of styreneand a conjugated diene, generally have limited practical utilityalthough known in the art.

The anionic polymerization of the conjugated diene hydrocarbons istypically controlled with structure modifiers such as diethylether orglyme (1,2-diethoxyethane) to obtain the desired amount of 1,4-addition.As described in U.S. Pat. No. Re 27,145 which is incorporated byreference herein, the level of 1,2-addition of a butadiene polymer orcopolymer can greatly affect elastomeric properties after hydrogenation.

The 1,2-addition of 1,3-butadiene polymers having terminal functionalgroups significantly and surprisingly influences the viscosity of thepolymers as described in more detail below. A 1,2-addition of about 40%is achieved during polymerization at 50° C. with about 6% by volume ofdiethylether or about 1000 ppm of glyme.

Dilithium initiation with the diadduct of sec-butyllithium (s-BuLi) andm-diisopropenylbenzene also requires presence of a non-reactivecoordinating agent such as diethyl ether, glyme, or triethyl amine,otherwise monolithium initiation is achieved. Ether is typically presentduring anionic polymerization as discussed above, and the amount ofether typically needed to obtain specific polymer structures has beensufficient to provide dilithium initiation.

Anionic polymerization is often terminated by addition of water toremove the lithium as lithium hydroxide (LiOH) or by addition of analcohol (ROH) to remove the lithium as a lithium alkoxide (LiOR). Forpolymers having terminal functional groups, the living polymer chainsare preferably terminated with hydroxyl, carboxyl, phenol, epoxy, oramine groups by reaction with ethylene oxide, carbon dioxide, aprotected hydroxystyrene monomer, ethylene oxide plus epichlorohydrin,or the amine compounds listed in U.S. Pat. No. 4,791,174, respectively.

Termination with ethylene oxide results in release of fine particles oflithium bases as described in U.S. patent application Ser. No.07/785,715 now U.S. Pat. No. 5,166,277 which is incorporated byreference herein. The lithium bases interfere with hydrogenation of thepolymer and preferably are removed.

Termination with carbon dioxide results in carboxylate salt groups thatreduce hydrogenation catalyst activity as described in U.S. Pat. No.4,970,254 which disclosure is incorporated by reference herein. Improvedhydrogenation is obtained by converting the carboxylate salt groups toester groups prior to hydrogenation and then reconverting to carboxylatesalt or carboxylic acid groups after hydrogenation.

Hydrogenation of at least 90%, preferably at least 95%, of theunsaturation in low molecular weight butadiene polymers is achieved withnickel catalysts as described in U.S. Pat. Nos. Re. 27,145 and 4,970,254and U.S. patent application Ser. No. 07/785715 which are incorporated byreference herein. The preferred nickel catalyst is a mixture of nickel2-ethylhexanoate and triethylaluminum described in more detail inExample 1 below.

Butadiene polymers having two or more terminal functional groupsselected from hydroxyl, carboxyl, phenol, epoxy, and amine groups can beused without solvents when the viscosity of the polymer is less thanabout 500 poise. These functional groups do not exhibit significantatomic attractions that would otherwise solidify the functionalizedpolymers. Hydrogenated butadiene polymers having a lower viscosity than500 poise are produced by limiting the peak molecular weight to a rangefrom 500 to 20,000 and by limiting the 1,2-addition to an amount between30% and 70%, preferably between 40% to 60%.

It is well known that the viscosity of higher molecular weight polymersis proportional to molecular weight raised to the 3.4 power as describedby D. W. Van Krevelen, "Properties of Polymers", Elsevier Scientific PubCo., New York, 1976, pp. 337-339, and J. D. Ferry, "ViscoelasticProperties of Polymers", John Wiley & Sons, New York, 1970, pp 267-271.For low molecular weight polymers having no functional groups, viscosityis proportional to molecular weight to the first power. Low molecularweight polymers having terminal functional groups behave like highermolecular weight polymers. Therefore, in comparing the viscosity of lowmolecular weight polymers having terminal functional groups, viscositydata must be adjusted for molecular weight variations by dividingmeasured viscosity by molecular weight raised to the 3.4 power.

The polymers of the invention have the conventional utilities such asforming coatings, sealants, and binders. In addition, the butadienepolymers having about two or more terminal hydroxyl groups can beco-polymerized with conventional compounds during production ofpolycarbonates, polyesters, and polyamides as described in U.S. Pat. No.4,994,526 which is incorporated herein by reference.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Hydrogenated 1,3-butadiene polymers having about two terminal groups permolecule and unexpectedly low viscosity have been produced bycontrolling the 1,2-addition of the butadiene. Such polymers are lowviscosity liquids at room temperature when the peak molecular weight ofthe polymer ranges between 1,000 and 10,000, as measured by gelpermeation chromatography using polybutadiene standards, and the1,2-addition ranges from 40% to 60%. The examples below show that1,2-addition of the hydrogenated butadiene polymers has an unexpectedeffect on viscosity.

The peak molecular weights were measured using gel permeationchromatography calibrated with polybutadiene standards having known peakmolecular weights. The solvent for all samples was tetrahydrofuran.

The 1,2-additions vinyl contents was measured by C¹³ NMR in chloroformsolution.

The viscosities were measured at room temperature on a RheometricsDynamic Mechanical Spectrometer in dynamic oscillatory mode at afrequency of 10 radians per second. Viscosity measurements were adjustedfor comparison by division with peak molecular weight raised to the 3.4power. Peak molecular weights are believed to best indicate molecularweight variations in the polymers of this invention and are determinedfrom standards having known peak molecular weights rather than byapproximation.

EXAMPLE 1

A linear hydrogenated butadiene polymer having about two terminalhydroxyl groups per molecule, a peak molecular weight of 2900, asdetermined by Gel Permeation Chromatography (GPC) using polybutadienestandards, and a 1,2-addition of 40%, as determined by a NuclearMagnetic Resonance (NMR) technique, was prepared as described below. Thelinear butadiene precursor polymer was synthesized using a diinitiatorfor the polymerization of 1,3-butadiene. The living polymer chain endswere capped using ethylene oxide to afford the precursor polymer havingterminal, primary hydroxyl functionality. This polymer was hydrogenatedusing a Ni/Al catalyst.

To synthesize the diinitiator moiety, 100 pounds of cyclohexane, 6pounds of diethyl ether, and 1564 g of m-diisopropenylbenzene (DIPB)(97% wt DIPB, 9.6 moles) were combined with stirring in a sealed, steelreactor vessel under an inert, nitrogen atmosphere. Impurities thatmight interfere with anionic polymerization were removed by titrationwith a solution of s-BuLi in cyclohexane (0.09 g of s-BuLi/ml). Thepurified solution was then treated with 2 equivalents of s-BuLi (23.5pounds of s-BuLi solution, 19 moles) for each equivalent of DIPB thatwas present. Reaction at 50° C. for 30 minutes gave a solution of theexpected diinitiator. The structure of the diinitiator was verified byanalyzing a methanol quenched aliquot of the solution using a gaschromatography-mass spectroscopy (GC-MS) technique.

In a separate vessel, 162 pounds of cyclohexane, 15 pounds of diethylether, and 42 pounds of polymerization grade 1,3-butadiene were combinedunder a nitrogen atmosphere at 20° C. As described above, the solutionwas titrated with s-BuLi reagent to remove impurities that wouldinterfere with the anionic polymerization of butadiene. The purifiedsolution of monomer was transferred to the vessel containing thediinitiator and polymerization ensued. The polymerization exotherm wascontrolled by cooling the reactor to keep the temperature of thereaction mixture below 50° C. After 30 minutes, the polymerizationreaction was essentially complete. An alpha, omega-polymer lithiumspecies (Li--B--Y--B--Li) had been synthesized.

The solution containing the diinitiated polymer was treated, at 50° C.,with 7.5 pounds of ethylene oxide (77 moles) to insert --C--C--O-- atthe polymer chain ends to form alkoxide polymer chain ends,--C--C--C--O--Li. Reaction was allowed to proceed for 3 hours. At thispoint, the reaction mixture was a solid rubbery mass resulting from theformation of an ionic gel derived from association of the alkoxidepolymer chain ends. Treatment of the gel with 610 g of methanol affordeda free flowing solution of a polybutadiene diol having --C--C--O--H endcaps and a precipitate of lithium methoxide (LiOMe). The precipitate wasallowed to settle in the reactor overnight.

A LiOMe slurry was drained from the bottom of the vessel and discarded.An aliquot of the clear solution of the butadiene polymer havingterminal hydroxyl groups was analyzed via GPC and found to contain asingle polymeric species having a peak molecular weight of 2900. Averagemolecular weights were calculated from the GPC data as M(n)=2470 andM(w)=2940.

Analysis by C(13)NMR found the 1,2-addition to be 40% and the ethyleneoxide end capping efficiency was 82% (100 times the ratio of moles of--C--C--O--H end caps to moles of s-BuLi initiator).

A 10 gallon aliquot of the solution of the butadiene polymer havingterminal hydroxyl groups was transferred to a high pressure reactor forhydrogenation using a Nickel/Aluminum catalyst. The catalyst wasprepared in advance by reacting nickel 2-ethylhexanoate withtriethylaluminum in cyclohexane in amounts sufficient to give a ratio of2.6 moles of aluminum to 1 mole of nickel. The polymer solution wassparged with hydrogen at 65° C. The reactor was then filled withhydrogen to a pressure of 810 psig. An initial aliquot of the Ni/Alcatalyst solution was then pressured into the reactor in such a volumeas to afford a Ni concentration of 100 ppm in the reaction mixture. Anexothermic hydrogenation reaction ensued.

When the temperature of the reaction solution had stabilized, an aliquotof the solution was analyzed by ozonolysis to check the degree ofhydrogenation of the polybutadiene diol. As hydrogenation wasincomplete, another aliquot of catalyst was added which lead to anadditional exotherm. This process was repeated until the ozonolysis testshowed essentially complete hydrogenation of the polybutadiene diol(final reaction conditions--[Ni]=1900 ppm, 95° C., 6 hr). An aliquot ofthe polymer solution was analyzed by C(13)NMR; by this method ofanalysis, 95% of the carbon-carbon unsaturation (--C=C--) had beenhydrogenated and there was no evidence of hydrogenolysis of the terminalhydroxyl groups.

The hydrogenation catalyst was removed from the polymer cement bycontacting with an excess of 1% by weight aqueous sulfuric acid solution(organic/aqueous=1/3(vol/vol)). The organic phase was washed repeatedlywith water to remove excess sulfuric acid. Ammonia gas was bubbledthrough the organic phase to ensure complete neutralization. Anantioxidant, Irganox 1076, was added to the cement in an amount toafford a concentration of 0.1% by weight in the final product. Thesolvent was removed from the polymer under vacuum affording a clear, lowviscosity liquid, hydrogenated butadiene polymer having about twoterminal hydroxyl groups per molecule. The properties of this sample arelisted in Tables 1 and 2 which follow the description of Examples 2-5below. Several commercial hydrogenated polybutadiene diols are includedfor comparison.

EXAMPLES 2-5

The procedure of Example 1 was modified to prepare a series ofhydrogenated butadiene polymers having about two terminal hydroxylgroups per molecule, different peak molecular weights, and differentamounts of 1,2-addition. The molecular weight of the diol was adjustedby varying the diinitiator to monomer ratio during polymerization of thebutadiene. The 1,2-addition was varied by adjusting the diethyl ethercontent of the solvent before polymerization and by adjusting thetemperature at which the butadiene polymerization was conducted. Higherlevels of 1,2-addition were favored by higher levels of diethyl etherand lower reaction temperatures. Synthesis in this way afforded productswith the structures of Table 1 and properties of Table 2.

                  TABLE 1                                                         ______________________________________                                        Example MW      1,2-Addition                                                                             EO Capping                                                                              Hydrogen-                                Number  (Peak)  (%)        Efficiency (%)                                                                          ation (%)                                ______________________________________                                        1       2900    40         82        95                                       2       3900    41         95        98                                       3       5060    40         92        99                                       4       3500    52         87        98                                       5       3970    48         85        99                                       POLY-   2300    84         NA        .sup. 99.sup.3                           TAIL HA.sup.1                                                                 NISSO   2380    84         NA        .sup. 98.sup.3                           GI-2000.sup.2                                                                 POLY-   3720    22         NA        NA                                       TAIL H.sup.1                                                                  ______________________________________                                         .sup.1 Polymer produced by Mitsubishi.                                        .sup.2 Polymer produced by Nippon Soda.                                       .sup.3 Measured by ozonolysis.                                           

                  TABLE 2                                                         ______________________________________                                        Example  MW      1,2-Addition                                                                             Viscosity                                                                            Adj. Viscosity                             Number   (Peak)  (%)        (poise)                                                                              (poise/MW.sup.3.4)                         ______________________________________                                        1        2900    40         155    0.26 × 10.sup.-9                     2        3900    41         836    0.52 × 10.sup.-9                     3        5060    40         2322   0.59 × 10.sup.-9                     4        3500    52         353    0.32 × 10.sup.-9                     5        3970    48         760    0.44 × 10.sup.-9                     POLYTAIL 2300    84         1650    6.1 × 10.sup.-9                     HA.sup.1                                                                      NISSO    2380    84         1480    4.9 × 10.sup.-9                     GI-2000.sup.2                                                                 POLYTAIL 3720    22         Solid.sup.3                                                                          --                                         H.sup.1                                                                       ______________________________________                                         .sup.1 Polymer produced by Mitsubishi.                                        .sup.2 Polymer produced by Nippon Soda.                                       .sup.3 Infinite viscosity at room temperature.                           

The relationship between viscosity and 1,2-addition for the hydrogenatedbutadiene polymers is plotted in FIG. 1 wherein the viscosity data isadjusted to remove molecular weight variations as described above.

For many applications such as coatings it is desirable to have polymersthat have terminal functional groups and have low viscosity at roomtemperature to allow application without any solvent, preferably at thehighest possible solids content. While it is known in the art thathydrogenated butadiene polymers having less than 30% 1,2-addition arecrystalline solids, Table 2 and FIG. 1 show that 1,2-addition between 30and 70% provides surprisingly low viscosities at room temperature forhydrogenated butadiene polymers having terminal groups. The polymers ofthe invention preferably have a ratio of viscosity (poise) to peakmolecular weight raised to the 3.4 power of at most 2.0×10⁻⁹, mostpreferably less than 1.0×10⁻⁹.

Results for Examples 2 and 3 validate the theoretical relationshipbetween viscosity and peak molecular weight. The ratios of viscosity topeak molecular weight raised to the 3.4 power for Examples 2 and 3 arealmost identical although the polymers have significantly differentmolecular weights and significantly different viscosities.

EXAMPLE 6 (Hypothetical)

A hydrogenated butadiene polymer having terminal hydroxyl groups isprepared as described in Example 1 except that the ratio of diinitiatorto butadiene monomer is adjusted to provide a peak molecular weight of10000.

EXAMPLE 7 (Hypothetical)

A hydrogenated butadiene polymer having terminal hydroxyl groups isprepared as described in Example 1 except that the ratio of diinitiatorto butadiene monomer is adjusted to provide a peak molecular weight of16000.

EXAMPLE 8 (Hypothetical)

A linear, hydrogenated butadiene polymer having a peak molecular weightof 4000, about two terminal carboxyl groups per molecule, and1,2-addition of 50% is produced by the procedure of Example 1 with thefollowing modifications.

Polymerization is conducted at 15° C. with 10% diethyl ether to obtain50% 1,2-addition.

The precursor butadiene polymer having terminal lithium atoms iscarboxylated by pumping the polymer solution through a pipeline reactorwherein the solution is contacted in a static mixer with high pressurecarbon dioxide. Efficient mixing and high pressure minimize coupling ofpolymer molecules.

The carboxylated polymer can be hydrogenated by the procedure of Example1 if a large excess of the nickel catalyst is used to overcome reducedactivity caused by the carboxyl groups. The carboxylated polymer ispreferably hydrogenated after esterification of the carboxylate groupswith methanol and an acid catalyst as described in U.S. Pat. No.5,002,676. After hydrogenation, the ester groups are converted back tocarboxylate groups by washing with a mixture a sulfuric acid/water whichalso removes the hydrogenation catalyst.

EXAMPLE 9 (Hypothetical)

A linear, hydrogenated butadiene polymer having a peak molecular weightof 4000, about two terminal amine groups per molecule, and 1,2-additionof 50% is produced by the procedure of Example 1 with the followingmodifications.

Polymerization is conducted at 15° C. with 10% diethyl ether to obtain50% 1,2-addition.

The precursor butadiene polymer having terminal lithium atoms isaminated by a ring opening reaction with a diaziridine,1,5-diazabicyclo[3.1.0]hexane as described in U.S. Pat. No. 4,753,991which is incorporated by reference herein. The polymer is hydrolyzed bytreatment with an excess of acetic acid (2 hours, 90° C.) and recoveredby coagulation in methanol.

Before hydrogenation, the amine terminated polymer is reacted incyclohexane with a slight excess of acetyl chloride (using pyridine as apromoter) to exhaustively acylate the amine groups to amide groups. Theamide groups are returned to amine groups during catalyst extractionwith aqueous sulfuric acid.

EXAMPLE 10 (Hypothetical)

A 1000 ml four neck flask is fitted with a mechanical stirrer, a pHprobe, an aqueous caustic inlet tube, and a Claisen adapter to whichthere is attached a dry ice condenser and a gas inlet tube. The flask ischarged with 400 ml of water, 500 ml of methylene chloride, 1.0 ml oftriethylamine, 2.0 g (0.0133 moles for 3.3 molar percent) ofp-tertiary-butylphenol, 5.0 g (0.0014 moles) of the hydrogenatedbutadiene polymer of Example 5, and 91.3 g (0.40 moles) of bisphenol-A.With stirring, phosgene is introduced into the flask at a rate of 1g/min for 50 minutes with the pH maintained in a range of 10.5 to 11.5by addition of 50% aqueous sodium hydroxide. The resin layer is thenseparated from the brine layer, washed with 3 wt % aqueous HCl untilwashing remains acidic, then twice washed with distilled water. Theresin is then precipitated into methanol in a Waring blender and washedwith methanol. The resin is useful as a molding resin to prepareexterior components of automobiles.

EXAMPLE 11 (Hypothetical)

Example 10 is repeated by replacing the hydrogenated butadiene polymerof Example 5 with 5.0 g (0.0005 moles) of the hydrogenated butadienepolymer of Example 6.

EXAMPLE 12 (Hypothetical)

Example 10 is repeated by replacing the hydrogenated butadiene polymerof example 5 with 5.0 g (0.0003 moles) of the hydrogenated butadienepolymer of Example 7.

EXAMPLE 13 (Hypothetical)

A 1000 ml four neck flask is fitted with a mechanical stirrer, a pHprobe, an aqueous caustic inlet tube, and a Claisen adapter to whichthere is attached a dry ice condenser and a gas inlet tube. The flask ischarged with 400 ml of water, 550 ml of methylene chloride, 0.5 ml oftriethylamine, 5.5 g (0.0016 moles) of the hydrogenated butadienepolymer of Example 5, and 65 g (0.285 moles) of bisphenol-A. Withstirring, phosgene is introduced into the flask at a rate of 0.75 g/minfor 36 minutes with the pH maintained in a range of 10.5 to 11.7 byaddition of 50% aqueous sodium hydroxide. The resin layer is thenseparated and washed as described in Example 10 from the brine layer,washed with 3 wt % aqueous HCl until washing remains acidic, then twicewashed with distilled water. The resin is then precipitated intomethanol in a Waring blender and washed with methanol. The resin isuseful as a molding resin to prepare gaskets.

EXAMPLE 14 (Hypothetical)

Example 13 is repeated by replacing the hydrogenated butadiene polymerof Example 5 with 5.5 g (0.00055 moles) of the hydrogenated butadienepolymer of Example 6.

EXAMPLE 15 (Hypothetical)

Example 13 is repeated by replacing the hydrogenated butadiene polymerof Example 5 with 5.5 g (0.0003 moles) of the hydrogenated butadienepolymer of Example 7.

EXAMPLE 16 (Hypothetical)

A 1000 ml four neck flask is fitted with a mechanical stirrer, a pHprobe, an aqueous caustic inlet tube, and a Claisen adapter to whichthere is attached a dry ice condenser and a gas inlet tube. The flask ischarged with 400 ml of water, 500 ml of methylene chloride, 3.0 ml oftriethylamine, 0.65 g (0.004 moles) of p-tertiary-butylphenol, 40.0 g(0.011 moles) of the hydrogenated butadiene polymer of Example 5, 30 g(0.131 moles) of bisphenol-A, and 45 g (0.083 moles) oftetrabromo-bisphenol-A. With stirring, phosgene is introduced into theflask at a rate of 1 g/min for 5 minutes at an initial pH of from 8.0 to9.0. Then phosgenation is continued for an additional 21 minutes whilemaintaining the pH within the range of 10.5 to 11.5 by addition of 50%aqueous sodium hydroxide. The resin layer is then separated from thebrine layer, washed with 3 wt % aqueous HCl until washing remainsacidic, then twice washed with distilled water. The resin is thenprecipitated into methanol in a Waring blender and washed with methanol.The resin is useful for extruding radio-opaque tubing for use as venouscatheters.

EXAMPLE 17 (Hypothetical)

Example 16 is repeated by replacing the hydrogenated butadiene polymerof Example 5 with 40.0 g (0.004 moles) of the hydrogenated butadienepolymer of Example 6.

EXAMPLE 18 (Hypothetical)

Example 16 is repeated by replacing the hydrogenated butadiene polymerof Example 5 with 40.0 g (0.0025 moles) of the butadiene polymer ofExample 7.

EXAMPLE 19 (Hypothetical)

A polyamide-hydrogenated butadiene block copolymer is produced byreacting 945.7 g (8.31 moles) of caprolactam, 4.3 g (0.029 moles) ofadipic acid, and 50 g (0.0145 moles) of the hydrogenated butadienepolymer of Example 5 in a 2 liter stainless steel reactor in thepresence of 1 g of catalyst (85% by weight phosphoric acid in water) at200° C. and a stirring speed of 200 rpm. After two hours of reaction,the reaction temperature is raised to 260 ° C. and a vacuum (0.5 mm Hg)was applied for two hours. The resulting resin is useful as a moldingcomposition to prepare exterior automotive components.

EXAMPLE 20 (Hypothetical)

A polyamide-hydrogenated butadiene block copolymer is produced by theprocess of Example 19 except that the reactants are varied to include674.2 g of the caprolactam, 25.8 g of the adipic acid, and 300 g of thehydrogenated butadiene polymer of Example 6.

EXAMPLE 21 (Hypothetical)

A polyamide-hydrogenated butadiene block copolymer is produced by theprocess of Example 19 except that the reactants are varied to include348.5 g of the caprolactam, 51.5 g of the adipic acid, and 600 g of thehydrogenated butadiene polymer of Example 7.

EXAMPLE 22 (Hypothetical)

A polyamide-hydrogenated butadiene block copolymer is produced byreacting 948.5 g of caprolactam, 1.5 g of adipic acid, and 50 g of thehydrogenated butadiene polymer of Example 5 in a 2 liter stainless steelreactor in the presence of 1 g of catalyst (85% by weight phosphoricacid in water) at 200° C. and a stirring speed of 200 rpm. After twohours of reaction, the reaction temperature is raised to 260° C. and avacuum (0.5 mm Hg) was applied for two hours. The resulting resin isuseful as a molding composition to prepare exterior automotivecomponents.

EXAMPLE 23 (Hypothetical)

A polyamide-hydrogenated butadiene block copolymer is produced by theprocess of Example 22 except that the reactants are varied to include691.2 g of the caprolactam, 8.8 g of the adipic acid, and 300 g of thehydrogenated butadiene of Example 6.

EXAMPLE 24 (Hypothetical)

A polyamide-hydrogenated butadiene block copolymer is produced by theprocess of Example 22 except that the reactants are varied to include382.5 g of the caprolactam, 17.5 g of the adipic acid, and 600 g of thehydrogenated butadiene polymer of Example 7.

EXAMPLE 25 (Hypothetical)

A polyamide-hydrogenated butadiene block copolymer is produced byreacting 949.1 g of caprolactam, 0.9 g of adipic acid, and 50 g of thehydrogenated butadiene polymer of Example 5 in a 2 liter stainless steelreactor in the presence of 1 g of catalyst (85% by weight phosphoricacid in water) at 200° C. and a stirring speed of 200 RPM. After twohours of reaction, the reaction temperature is raised to 260° C. and avacuum (0.5 mm Hg) was applied for two hours. The resulting resin isuseful as a molding composition to prepare exterior automotivecomponents.

EXAMPLE 26 (Hypothetical)

A polyamide-hydrogenated butadiene block copolymer is produced by theprocess of Example 25 except that the reactants are varied to include694.5 g of the caprolactam, 5.5 g of the adipic acid, and 300 g of thehydrogenated butadiene of Example 6.

EXAMPLE 27 (Hypothetical)

A polyamide-hydrogenated butadiene block copolymer is produced by theprocess of Example 25 except that the reactants are varied to include389.0 g of the caprolactam, 11.0 g of the adipic acid, and 600 g of thehydrogenated butadiene of Example 7.

EXAMPLE 28 (Hypothetical)

A polyamide-hydrogenated butadiene block copolymer is produced byrefluxing 419.7 g (3.62 moles) of hexamethylene diamine, 530.3 g (3.62moles) of adipic acid, and 50 g (0.0145 moles) of the hydrogenatedbutadiene polymer of Example 5 in a resin kettle at a temperaturebetween 120° to 150° C. for 3 hours under a nitrogen blanket. Themixture is then gradually heated from reflux temperature to 200° C.while water is removed by distillation. Six drops of phosphoric acid areadded, and the mixture is heated at 220° to 240° C. under a vacuum of0.05 to 5 mm Hg for 3 hours. The resulting copolymer is allowed to coolto room temperature. The resin is useful as a component for exteriorautomotive applications.

EXAMPLE 29 (Hypothetical)

A polyamide-hydrogenated butadiene block copolymer is produced by theprocess of Example 28 except that the reactants are varied to include350.4 g of the hexamethylene diamine, 449.5 g of the adipic acid, and200 g of the hydrogenated butadiene polymer of Example 5.

EXAMPLE 30 (Hypothetical)

A polyamide-hydrogenated butadiene block copolymer is produced byrefluxing 420.3 g of hexamethylene diamine, 529.7 g of adipic acid, and50 g of the hydrogenated butadiene polymer of Example 6 in a resinkettle at a temperature between 120° to 150° C. for 3 hours under anitrogen blanket. The mixture is then gradually heated from refluxtemperature to 200° C. while water is removed by distillation. Six dropsof phosphoric acid are added, and the mixture is heated at 220° to 240°C. under a vacuum of 0.05 to 5 mm Hg for 3 hours. The resultingcopolymer is allowed to cool to room temperature. The resin is useful asa component for exterior automotive applications.

EXAMPLE 31 (Hypothetical)

A polyamide-hydrogenated butadiene block copolymer is produced by theprocess of Example 30 except that the reactants are varied to include352.9 g of the hexamethylene diamine, 447.1 g of the adipic acid, and200 g of the hydrogenated butadiene polymer of Example 6.

EXAMPLE 32 (Hypothetical)

A polyamide-hydrogenated butadiene block copolymer is produced byrefluxing 420.4 g of hexamethylene diamine, 529.6 g of adipic acid, and50 g of the hydrogenated butadiene polymer of Example 7 in a resinkettle at a temperature between 120° to 150° C. for 3 hours under anitrogen blanket. The mixture is then gradually heated from refluxtemperature to 200° C. while water is removed by distillation. Six dropsof phosphoric acid are added, and the mixture is heated at 220° to 240°C. under a vacuum of 0.05 to 5 mm Hg for 3 hours. The resultingcopolymer is allowed to cool to room temperature. The resin is useful asa component for exterior automotive applications.

EXAMPLE 33 (Hypothetical)

A polyamide-hydrogenated butadiene block copolymer is produced by theprocess of Example 32 except that the reactants are varied to include353.4 g of the hexamethylene diamine, 446.6 g of the adipic acid, and200 g of the hydrogenated butadiene polymer of Example 7.

EXAMPLE 34 (Hypothetical)

A polyester-hydrogenated butadiene block copolymer is produced bycharging into a 1 liter reaction kettle 45.0 g of 1,4-butanediol, 3.8 gof the hydrogenated butadiene polymer of Example 7, 48.5 g of dimethylterephthalate, 0.129 g of titanium butoxide, and 0.129 g of Irganox1098, an antioxidant. Transesterification of the reactants is carriedout at 180° C. for 2.5 hours under a nitrogen blanket. The methanolreleased by the reaction is collected in a condenser. The temperature isthen raised to 245° C. to start polymerization. Vacuum is applied slowlyover a 15 minute period to 0.15 mm Hg. About one-half of the1,4-butanediol is distilled off and then polymerization is continued for3 hours. The resulting polymer is useful as a molding compound forexterior automotive components.

EXAMPLE 35 (Hypothetical)

A polyester-hydrogenated butadiene block copolymer is produced by theprocess of Example 34 except that the reactants are modified to contain30.6 g of the hydrogenated butadiene polymer of Example 5.

EXAMPLE 36 (Hypothetical)

A polyester-hydrogenated butadiene block copolymer is produced by theprocess of Example 34 except that the reactants are modified to contain107.3 g of the hydrogenated butadiene polymer of Example 5.

EXAMPLE 37 (Hypothetical)

A polyester-hydrogenated butadiene block copolymer is produced bycharging into a 1 liter reaction kettle 45.0 g of 1,3-propanediol, 3.6 gof the hydrogenated butadiene polymer of Example 5, 48.5 g of dimethylterephthalate, 0.129 g of titanium butoxide, and 0.129 g of Irganox1098, an antioxidant. Transesterification of the reactants is carriedout at 180° C. for 2.5 hours under a nitrogen blanket. The methanolreleased by the reaction is collected in a condenser. The temperature isthen raised to 245° C. to start polymerization. Vacuum is applied slowlyover a 15 minute period to 0.15 mm Hg. About one-half of the1,3-propanediol is distilled off and then polymerization is continuedfor 3 hours. The resulting polymer is useful as a molding compound forexterior automotive components.

EXAMPLE 38 (Hypothetical)

A polyester-hydrogenated butadiene block copolymer is produced by theprocess of Example 37 except that the reactants are modified to contain28.9 g of the hydrogenated butadiene polymer of Example 5.

EXAMPLE 39 (Hypothetical)

A polyester-hydrogenated butadiene block copolymer is produced by theprocess of Example 37 except that the reactants are modified to contain101.3 g of the hydrogenated butadiene polymer of Example 5.

EXAMPLE 40 (Hypothetical)

A polyester-hydrogenated butadiene block copolymer is produced bycharging into a 1 liter reaction kettle 31.0 g of 1,2-ethanediol, 3.4 gof the hydrogenated butadiene of Example 5, 48.5 g of dimethylterephthalate, 0.129 g of titanium butoxide, and 0.129 g of Irganox1098, an antioxidant. Transesterification of the reactants is carriedout at 180° C. for 2.5 hours under a nitrogen blanket. The methanolreleased by the reaction is collected in a condenser. The temperature isthen raised to 245° C. to start polymerization. Vacuum is applied slowlyover a 15 minute period to 0.15 mm Hg. About one-half of the1,2-ethanediol is distilled off and then polymerization is continued for3 hours. The resulting polymer is useful as a molding compound forexterior automotive components.

EXAMPLE 41 (Hypothetical)

A polyester-hydrogenated butadiene block copolymer is produced by theprocess of Example 40 except that the reactants are modified to contain27.4 g of the hydrogenated butadiene polymer of Example 5.

EXAMPLE 42 (Hypothetical)

A polyester-hydrogenated butadiene block copolymer is produced by theprocess of Example 40 except that the reactants are modified to contain96.0 g of the hydrogenated butadiene polymer of Example 5.

EXAMPLE 43

A polyurethane coating was prepared by placing 54.1 parts by weight(pbw) of the hydroxyl terminated, hydrogenated polybutadiene diol ofExample 3, 0.01 pbw of dibutyl tin dilaurate and 36.0 pbw of tolueneinto a jar. The jar was capped and placed on a shaker for 30 minutes.Then 9.9 pbw of the isocyanate DESMODUR Z-4370 (ex. Miles) were added tothe jar and the jar was returned to the shaker for 30 minutes. Thismixture was applied with a paint brush to a steel panel. Afterdrying/curing for 2 weeks at room temperature, the coated film wasuseful as a clear, elastomeric, polyurethane coating.

EXAMPLE 44

A polyurethane coating was prepared by placing 33.6 pbw of thehydrogenated polybutadiene diol of Example 3, 0.004 pbw of dibutyl tindilaurate, 22.4 pbw of toluene, and 37.9 pbw of the titanium dioxideTI-PURE R-902 (ex. DuPont) into a jar. Grinding grit was then added tothe jar. This mixture was rolled on a bottle roller until the TiO₂particle size was reduced to a Hegman 6 "fineness of grind". This tookabout 3 days of rolling the jar. The blend was filtered to remove thegrinding grit. To 93.9 pbw of this blend was added 6.1 pbw of theisocyanate DESMODUR Z-4370. After thoroughly mixing in the isocyanate,the mixture was applied with a 10 mil doctor blade onto a steel panel.After drying/curing for 2 weeks at room temperature, the coated film wasuseful as a white, elastomeric, polyurethane coating.

EXAMPLE 45 (Hypothetical)

An isocyanate terminated prepolymer is prepared by placing 44.3 pbw ofthe hydrogenated polybutadiene diol of Example 5, 5.7 pbw of a diphenylmethane diisocyanate (2/1 NCO/OH), and 50 pbw of toluene into a jar andgently rolling the jar for 2 weeks at room temperature. Then 100 pbw ofthis prepolymer is mixed with 50 pbw of WINGTACK 95 hydrocarbontackifying resin (ex. Goodyear) and 100 pbw of ATOMITE calcium carbonate(ex. Thompson Weiman) in a sigma blade mixer under a dry nitrogenblanket. The material is then packaged with critical exclusion ofmoisture until the package is opened for use. The material is useful asa moisture-curable, polyurethane/urea sealant, caulk, or coating.

EXAMPLE 46 (Hypothetical)

An acrylate terminated prepolymer is prepared by placing 3.5 pbw ofhydroxy ethyl acrylate, 6.7 pbw isophorone diisocyanate (2/1 NCO/OH),0.007 pbw dibutyl tin dilaurate, and 30 pbw xylene into a resin kettle.With gentle stirring, this mixture is heated to 80° C. and held for 3hours. Then 59.8 pbw of the hydrogenated polybutadiene diol from Example5 is added and heating is continued for another 3 hours at 80° C. togive the acrylate terminated prepolymer. This material is useful incoatings, sealants, and adhesives which are cured by free radicalprocesses, initiated for example by peroxides or radiation.

EXAMPLE 47 (Hypothetical)

A water-borne polyurethane/urea dispersion is prepared by charging 53.1pbw of the hydrogenated polybutadiene diol of Example 5, 14.0 pbw of theisocyanate DESMODUR W (ex. Miles), 3.5 pbw of dimethylol propionic acid,and 23.6 pbw of xylene to a resin kettle. This mixture is heated to 80°C. and is held for 4 hours to prepare the isocyanate terminatedprepolymer. Then 2.7 pbw of triethyl amine is added to ionize the acidgroups and heating is continued for another hour. This product is thendispersed in 290 pbw of water and 3.1 pbw of DYTEK A is quickly added.Heating at 80° C. is continued for another hour to chain extend theprepolymer giving the water-borne polyurethane/urea dispersion. Thismaterial is useful as a low VOC coating.

EXAMPLE 48

A bake-cured coating was prepared by mixing 40 pbw of the hydrogenatedpolybutadiene diol of Example 3, 9 pbw CYMEL 303 hexamethoxy melamineresin (ex. American Cyanamid), 1 pbw of CYCAT 600 acid catalyst (ex.American Cyanamid), and 50 pbw of toluene in a jar on a bottle rollerovernight. Coatings about 2 mils thick were cast on polyester film witha 10 mil doctor blade. The coatings are cured for 10, 20, or 30 minutesin an oven at 150° C. Gel contents measured on these films were 81%,84%, and 92%, respectively. (Gel content is the percentage of materialin the coating which is insoluble in toluene after the coating isbaked.) These compositions should be useful in amino resin curedcoatings.

EXAMPLE 49 (Hypothetical)

A saturated polyester resin (1.3/1 OH/COOH) is prepared by charging 55.5g of the hydrogenated butadiene diol of Example 3, 102.3 g of neopentylglycol, 9.9 g of trimethylol propane, 70.4 g of isophthalic acid, 61.9 gof adipic acid, 0.40 g of dibutyl tin dilaurate, and 30 g of xylene to a500 ml resin kettle equipped with a stirrer and a partial condenser. Theingredients are carefully heated to 230° C. under a nitrogen purge. Theesterification reaction is continued at 230° C. for 6 hours. Aftercooling to room temperature, the product is a sticky, opaque mass. Theproduct is useful as a toughened, high solids, hydroxyl terminated,polyester resin for coatings.

We claim:
 1. A polymer, consisting essentially of:polymerized1,3-butadiene having a peak molecular weight between 500 and 20,000,1,2-addition between 30% and 70%, and hydrogenation of at least 90% ofthe unsaturation; and one or more terminal functional groups permolecule.
 2. The polymer of claim 1, wherein the terminal functionalgroups are selected from a group consisting of hydroxyl, carboxyl,phenol, epoxy, and amine groups.
 3. The polymer of claim 2, wherein thepolymer has a ratio of viscosity (poise at room temperature) to peakmolecular weight raised to the 3.4 power of at most 2.0×10⁻⁹.
 4. Thepolymer of claim 3, wherein the polymerized butadiene has a peakmolecular weight between 1,000 and 10,000.
 5. The polymer of claim 4,wherein the polymerized butadiene is at least 95% hydrogenated.
 6. Thepolymer of claim 5, wherein the ratio of viscosity to peak molecularweight raised to the 3.4 power is less than 1.0×10⁻⁹.
 7. The polymer ofclaim 6, wherein the terminal functional groups consist of about twohydroxyl groups per molecule.
 8. The polymer of claim 1, wherein thepeak molecular weight is between 1000 and
 10000. 9. The polymer of claim8, wherein the 1,2-addition of the polymerized butadiene is between 40%and 60%.
 10. A polymer, comprising:polymerized 1,3-butadiene having apeak molecular weight between 500 and 20000, hydrogenation of at least90% of the unsaturation, and 1,2-addition between 30% and 70%; and abouttwo terminal functional groups per molecule.
 11. The polymer of claim10, wherein the terminal functional groups are selected from a groupconsisting of hydroxyl, carboxyl, phenol, epoxy, and amine groups. 12.The polymer of claim 11, wherein the polymerized butadiene is at least95% hydrogenated.
 13. The polymer of claim 12, wherein the ratio ofviscosity (poise at room temperature) to peak molecular weight raised tothe 3.4 power is at most 2.0×10⁻⁹.
 14. The polymer of claim 13, whereinthe terminal functional groups are hydroxyl groups.
 15. The polymer ofclaim 14, wherein the peak molecular weight is between 1000 and 10000.16. The polymer of claim 15, wherein the 1,2-addition of the polymerizedbutadiene is between 40% and 60%.